This work deals with carborane and metallacarborane clusters, in terms of their fundamental chemistry and complexation with cyclodextrins, and in the context of emerging pharmacophores applicable in medicinal chemistry. Arguably, the most important part of this work is the preparation of cobalt bis(dicarbollide) sulfamide derivatives. The sulfamido group is attached to the metallacarborane carbon vertex by an alkyl chain that may be modified in its length. This was accomplished by, firstly, the abstraction of the acidic hydrogen, located on the {CH}-vertex from the metallacarborane, by reaction with lithium base, followed by, secondly, reaction with electrophilic agents (PFA, oxirane and oxetane), which leads to a cascade of reactions to give the desired sulfamide derivatives. These compounds were then tested by collaborators in other institutes for in vitro and in vivo activity towards Carbonic Anhydrase IX (CA IX), which is an enzyme associated with tumour growth. In vivo tests on mice have shown that these types of substances are able to effectively reduce tumour size by 30%. The synthetic research continued with the preparation of sulfonamide compounds of the isomers of the carborane series. The reactions began exclusively with propylhydroxy carborane starting materials, which provide optimum...

This work deals with carborane and metallacarborane clusters, in terms of their fundamental chemistry and complexation with cyclodextrins, and in the context of emerging pharmacophores applicable in medicinal chemistry. Arguably, the most important part of this work is the preparation of cobalt bis(dicarbollide) sulfamide derivatives. The sulfamido group is attached to the metallacarborane carbon vertex by an alkyl chain that may be modified in its length. This was accomplished by, firstly, the abstraction of the acidic hydrogen, located on the {CH}-vertex from the metallacarborane, by reaction with lithium base, followed by, secondly, reaction with electrophilic agents (PFA, oxirane and oxetane), which leads to a cascade of reactions to give the desired sulfamide derivatives. These compounds were then tested by collaborators in other institutes for in vitro and in vivo activity towards Carbonic Anhydrase IX (CA IX), which is an enzyme associated with tumour growth. In vivo tests on mice have shown that these types of substances are able to effectively reduce tumour size by 30%. The synthetic research continued with the preparation of sulfonamide compounds of the isomers of the carborane series. The reactions began exclusively with propylhydroxy carborane starting materials, which provide optimum...

Compounds with carboxylic and amidic functions belong to basic structural blocks, which are used for construction of functional molecules in organic, organometallic and also in carborane chemistry. However, considering cobalt bis(dicarbollide)(1-) ion, the synthetic ways to these derivatives have been virtually unknown. A published procedure on lithiation in THF and reaction with CO2 leading to mono- and dicarboxylic acids had failed in our hands. Nevertheless, a detailed revision of the experimental conditions provided finally good yields of mixture of both acids, which could be separated by chromatography and crystallization, and compound of general formulation [(1-HOOC-1,2-C2B9H10)(1',2'-C2B9H10)-3,3'-Co(III)]- and stereoisomeric mixture of [(HOOC)2-(1,2-C2B9H10)2-3,3'-Co(III)]- were characterized for the first time by combination of NMR, MS and HPLC. Also, the carboxylic acid derivatives with methylene and ethylene connectors of the general formula [(1-HOOC-(CH2)n-1,2- C2B9H10)(1',2'-C2B9H10)-3,3'-Co(III)]- were prepared by lithiation of Cs1 in DME at low temperatures followed by reaction with BrCH2COOEt and subsequent hydrolysis of the resulting ester or by oxidation of the respective propylhydroxy derivative. The acids were converted to reactive p-nitrophenyl esters...